Emulsions and Suspensions

Colloidal Systems
• Colloids are mixed systems in which one (or
more) substance is dispersed in another
• Colloids are not solutions. Two distinct
phases can be determined
• Large molecules or subdivided matter
> 10-9 – 10-6m
Two-Phase Colloidal Systems
Continuous phase Dispersed phase Name

Gas Liquid Fog, mist, aerosol

Gas Solid Smoke, aerosol

Liquid Gas Foam

Liquid Liquid Emulsion

Liquid Solid Sol, gel, suspension

Solid Gas Solid foam

Solid Liquid Gel, solid emulsion

Solid Solid Alloy

Solution

Suspension

Foam
Gel

Emulsions
Solid foam
 Emulsions
• One liquid phase dispersed in another
• Typically water and oil involved

Dispersed phase
(typically 0.1-50µm)
Continuous phase
 Examples
• Oil-in-water (o/w)
• Salad dressing, mayonnaise
• Non-polar flavor components in beverages
• Milk
• Cake batter

• Water-in-oil (w/o)
• Butter
• Margarine
 O/W Emulsions

http://www.foodsci.uoguelph.ca/
 Italian Salad Dressing

Traditional Light Traditional Light

Light (less oil, 14% carbohydrate)

w/o Emulsion
Fat crystalline network (yellow) and a water
droplet structure (blue) in margarine
observed by Cryo-Scanning EM. Empty
spaces are where oil used to be.

http://www.isaac-heertje.nl/
 Interfacial Energy
• Immiscible (polar and non-polar) components tend
to limit area of contact (interface)
• To create interface requires work
W = γΔA
where γ is the interfacial tension
• The smaller the droplets formed, the more area,
thus more work is involved
 oil work = γΔA

aqueous
phase

The interfacial energy γ describes the amount of work

required to create unit area of interface (units mN m-1)

Surface tension occurs between liquids and air

 Least area in common
Most thermodynamically
stable

More area in common

Less thermodynamically
work
stable

work

Most area in common

Least thermodynamically
stable
Most kinetically stable
 Emulsifiers
• Ingredients known as emulsifiers can
be used to lower the interfacial
energy between phases
• Typically, these have both hydrophilic
and lypophilic groups which can orient
in each phase
• Low MW detergent-like molecules

CH2-OCO-
CHOH
CH2-OH Non-polar tail

Polar head

Regions with hydrophobic amino acids

• Unfolded proteins
 Common Emulsifiers

• Mono- and di-glycerides (low HLB)

• Sorbitan esters of fatty acids (SPANS)
• Polyoxyethylene sorbitan esters of fatty acids
(TWEENS)
• Ethoxylated mono- and di-glycerides
• Lecithin (“natural” source)
• Proteins
Sorbitan tristearate (SPAN 15) Diglycerol monostearate

Glycerol monostearate Poloxyethylene sorbitan monostearate

Sorbitan monostearate

Sodium stearoyl-2-lactylate
Important Food Emulsifiers
Class Emulsifier Emulsion Type Application
Protein Caseinate o/w Ice cream
Whey protein o/w Cake batter
Egg protein o/w Mayonnaise
Polysaccahride Methyl cellulose o/w Artificial cream

Propylene glycol o/w Salad dressing

alginate

Small molecules Monoglycerides w/o Margarine

Acid esters of w/o and o/w Baked products
Source:
Darling and Birkett, 1986 Sorbitan esters w/o Confections
Polyoxyethlene o/w Toppings
derivatives
Lecithin o/w & w/o Milk powder
Hydrophilic-Lipophilic Balance (HLB)
• Generally the emulsifier is more soluble in
the continuous phase
• Some emulsifiers are better for o/w
emulsions, some for w/o emulsions
• HLB describes relative amount of
hydrophilic and lipophilic character based
on solubility in each phase
• Solubility in water increases with HLB
 HLB of Common Emulsifiers
Emulsifier HLB
More oil soluble
Sorbitan tristearate (SPAN 15) 2.1
Propylene glycol monostearate 3.4
Glycerol monostearate 3.8 Promote w/o
emulsions
Sorbitan monooleate (SPAN 80) 4.3
Sorbitan monostearate (SPAN 60) 4.7
Succinic acid esters of monglyceride 5.3
Wetting agent
Diglycerol monostearate 5.5
Tetraglycerol monostearate 9.1 Promote o/w
emulsions
Diacetyl tartaric ester of monglyceride 9.2
Poloxyethylene sorbitan monostearate 14.9
(TWEEN 60) Detergent,
Poloxyethylene sorbitan monooleate 15.0
solubilizer
(TWEEN 80)
More water soluble
Sodium stearoyl-2-lactylate 21.0
 Forming Emulsions
• Considerable work is required to break up
one phase into fine droplets
• Emulsifiers help decrease the work needed
• Large droplets initially formed, then broken
up into finer droplets. Tremendous shearing
forces needed to create small droplets and
overcome large pressure difference

ΔP = 4γ
d
• Laboratory
– High-speed mixers
– Ultrasonic homogenizer (cavitation)

• Large-scale
– Valve homogenizer
 Valve
Pressure

Impact
Ring

Homogenized
Product

Seat

Raw Product
 2nd
Stage

Homogenized Product

Raw Product

1st
Stage
Animation at: http://gbm.dk/gbm/Valve-e.htm

Manton-Gaulin homgenizer
http://www1.lsbu.ac.uk/water/enztech/pressurec.html
Microscope View

1-stage 2-stage
unhomogenized (2500 psig) (2500/500 psig)

Range: 1-50 µm Range: 0.2-2 µm Range: 0.2-2 µm

Clusters form No clusters

Source: www.foodsci.uoguelph
 2 Piston
Homogenizer

Benchtop
Homogenizer

Emulsiflex
Emulsifers can help decrease particle size

After a critical concentration is

reached, droplet size depends only on
the homogenization energy

Corn oil in water Panndolfe (1995)

 Effect of Multiple Passes

More passes can create smaller droplets and more uniform droplet size
 Emulsion Stability
• Emulsions are thermodynamically
unstable. Energy of the dispersed
system is higher than that of the
separated phases
• Efforts geared towards controlling
rate of destabilization
 Types of Instability

• Sedimentation/Creaming: dispersed
phase moves down (sedimentation) or up
(creaming) due to density differences

• Flocculation: particles aggregate

together without change in droplet size.
More easily redispersed
• Coalescence: droplets fuse together in
to larger entities

• Phase inversion: change from an o/w

to a w/o emulsion
Creaming/Sedimentation
• Due to density differences between
water and less dense oil phase.
• At low phase volume φ, Stoke’s law
describes the velocity of moving
particles g = gravitational constant
ρw = density of aqueous phase

g(ρw – ρo)d2 ρo = density of oil phase

υs =
18ηo d = diameter of dispersed droplet
ηo = viscosity of continuous phase
 time velocity υ

The oil rises over time

At greater volume fraction (0.01<φ<0.05)

υ = υ s(1- φ)/[1- φ1/3]exp[5 φ /3(1- φ)]

Creaming/sedimentation is decreased by
– making smaller droplets (↓d)
– increase viscosity of continuous phase (↑ηo)
– decrease density difference (ρw – ρo )
e.g. brominated oils,
BVO banned in some countries
“Interim” food additive in the U.S.
 Flocculaton
• Droplets attracted to each other through
– Attractive force: long-range van der Waals

– Repulsive force:
• electric charges on droplets
• surrounding counterions (electric double layers)
• steric repulsion from absorbed polymers

• To prevent flocculation, attractive forces

must be balanced by repulsive forces
time
Potential Energy Between Two Droplets
60
40 Electrostatic Repulsion
Potential Energy (kT)

20
0
-20
-40
-60
Van der Waals Attraction

0 5 10 15 20 25

Separation Distance (nm)

• Van der Waals forces tend to bring the particles
close enough together
• At close distances they are very strong and tend
to hold the particles together
• Particles with a surface charge repel each other
• If the particles get close enough, the attractive
forces dominate
Stabilization
- - - -
+ -
- -
- + + - - + + +
+ + + -
- + - - + +
+
-
+ + - ++ +
-
+ + + +
- + + +
+ + - - - - +
- - -
- -
Stabilized by charge repulsion
from electric double layers
formed by counterions
Stabilized by steric repulsion of
macromolecules absorbed at
Electrostatic
Potential
droplet interface
Ψ
• Distance of electric double layer described by the
Debye-Huckel length (κ-1)

4.31 x 10 -10

κ =
-1
2I 1/2

– The double layer thickness is inversely related to the ionic strength I.

Thus, added salts!thinner double layers! tend to promote flocculation

• High surface concentration of protein may promote

stabilization by steric hindrance through
– “Osmotic effects”
– Volume restriction
– Part of the polymer must absorb strongly
– In some cases, polymers “bridge” droplets leading
to destabilization
 Coalescence
• Two or more droplets fuse together to form
larger entities. Usually undesirable and
unacceptable by consumers.
• Occasionally useful:
– Enhance flavor release during chewing
– Coalescence of semi-crystalline fat during cream
turning
• Usually occurs after creaming or flocculation
time
 Liquid film lamella

Droplets
approach

Lamella drains due to capillary

forces. Surfactant swept along
interface.
Lamella ruptures.
Droplets coalesce.
Coalescence enhanced by presence of
particles in the dispersed droplets:

• Semi-crystalline fat in oil phase

• Aggregated protein in aqueous phase

Coalescence may be decreased by:

• Absorbed proteins which enhance surface
viscosity
• Polysaccharides in the continuous phase
 Miscroscopic observation of the droplet
size evolution of a silicone-in-water
emulsion stabilized by Lauropal 205 (a, 1
h; b, 2 h; c, 3 h; and d, 4 h), the
temperature being 80°C.

Current Opinion in Colloid & Interface

Science Vol 4, Issue 3, 1 June 1999,
Pages 223–230
 Factors Affecting Stability and Rheology
Factor Creaming Flocculation Coalescence Rheology
Droplet size 3 2 1 1
Droplet size distribution 3 2 0 2
Droplet volume fraction 3 3 3 3
Density difference between 3 0 0 0
phases
Rheology of continuous phase 3 3 2 3
Rheology of dispersed phase 0 0 0 1
Rheology of absorbed layer 0 0 3 2
Thickness of absorbed layer 1 2 3 2
Electrostatic interactions 1 3 2 1
Steric polymeric interactions 0 3 2 2
Fat crystallization 0 0 3 3
Liquid crystalline phases 1 1 2 2
0 = not important 2 = often important From Dickerson, 1992
1 = sometimes important3 = generally important
Characterizing Emulsions
Important characteristics include
• Average particle size
• Particle size distribution
• Apparent viscosity
• Stability
 Particle Size Distribution
Various methods exist for measuring
particle size and distribution:
• Direct microscopic observation
– Can detect particles down to 0.5 – 1.0 µm
– Electron microscopy
– Light scattering
 Water droplets Casein

Fat

Butter Milk
Visible light TEM

Source: University of Guelph website

 Chocolate Mayonnaise
Confocal Microsocpe SEM
Crystallized fat Oil

Ice Cream Salad Dressing

TEM Confocal (Oil with fluorescent stain)
 Water (dark)

Dodecane in water/glycerol
Confocal
www.physics.emory.edu/ ~weeks/lab/emulsion/

Lowfat spread
Oil in water in oil emulsion !!
Generally particles are not uniform in
size but form a distribution of sizes
Frequency

0.5 1.0 1.5 2.0 2.5 3.0

Diameter (µm)
Image Analysis
• Images can be saved as digital files or
scanned
• Image software allows image
enhancement